Chemical Compositions of Brassica rapa L.
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摘要:
目的 研究芜菁的化学成分,发现其活性成分。 方法 芜菁经甲醇回流提取、硅胶柱层析、薄层层析、Sephadex LH-20柱层析进行分离纯化,波谱分析(核磁共振氢谱、碳谱)确定结构谱。 结果 从该药用植物分离得到17个化合物,分别为:(1) 1-(4-羟基苯基)-2-丙酮;(2) 4-(2-丁氧基乙基)苯酚;(3) 1-甲氧基-3-吲哚乙腈; (4) 2,2′-oxybis(1,4)-di-tert-butylbenzene;(5) 单棕榈酸甘油酯;(6) 邻苯二甲酸-1-丁酯-2-异丁酯;(7) 邻苯二甲酸二丁酯;(8) 1-甲氧基-3-吲哚甲醛;(9) 3,7-Dimethyl-n-octan-3α-ol-1-yl-benzoate; (10) 邻苯二甲酸二(2-乙基)己酯; (11) β-谷甾醇;(12) TgSSTg;(13) 3-吲哚甲醛;(14) 咖啡酸;(15) 槲皮素;(16) auriculatumA;(17)甘草黄苷。 结论 1~5、8~9、12~13均为首次从该植物分离得到。以上化合物的发现进一步丰富了芜菁的化学成分组成,为综合开发和利用芜菁植物资源提供前期的实验基础。 Abstract:Objective To study the chemical constituents of Brassica rapa L. and find its active components. Methods The chemical constituents of Brassica rapa L. were extracted by methanol reflux, separated and purified by silica gel column chromatography, thin layer chromatography and Sephadex LH-20 column chromatography, and the structural spectrum was determined by spectral analysis (nuclear magnetic resonance hydrogen spectrum, carbon spectrum). Results Seventeen compounds were isolated and identified as: (1) 1-(4-hydroxyphenyl )-2-propanone; (2) 4-(2-butoxyethyl) phenol; (3) 1-methoxy-3-indoleacetonitrile; (4) 2, 2′-oxybis(1, 4)-di-tert-butylbenzene; (5) Glycerol monopalmitate; (6) 1-butyl phthalate-2-isobutyl phthalate; (7) Dibutyl phthalate; (8) 1-methoxy-3-indole formaldehyde; (9) 3, 7-Dimethyl-n-octan-3α-ol-1-yl-benzoate; (10) Di(2-ethylhexyl) phthalate; (11) β-sitosterol; (12) TgSSTg; (13) 3-Indolecarboxaldehyde; (14) Caffeic acid; (15) Quercetin; (16) auriculatum A; (17) Liquiritin. Conclusion 1~5, 8~9, 12~13 were isolated from this plant for the first time. The discovery of the above compounds further enriched the chemical compositionof Brassica rapa L. and provided a preliminary experimental basis for the comprehensive development and utilization of Brassica rapa L. plant resources. -
Key words:
- Brassica rapa L. /
- Chemical constituents /
- Isolation and identification
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芜菁(Brassica rapa L.),又称蔓菁,藏药名为妞玛,是十字花科(Brassicaceae)芸薹属(Brassica)两年生草本植物。芜菁的根、叶、种子均可入药,藏医学经典著作《四部医典》记载,芜菁味甘性温,化味甘,块根“祛风、生‘赤巴’、滋补、解毒,治‘培根病’、‘龙病’、虚弱”,具有清热解毒、滋补增氧功效,治疗培根病、身体虚弱等症;种子解毒,具有治各种食物中毒等功效[1]。《补缺肘后方》记载芜菁根大者,削去上皮,熟捣,苦酒和如泥,煮三沸,急搅之,出,敷肿,帛裹上,日再三易,可治卒毒肿起,急痛;《千金方》记载:不中水芜菁叶,烧作灰,和猪脂敷之可治小儿头秃疮[2]。现代药理学研究表明芜菁在抗缺氧[3]、抗氧化[4-5]、抗癌[6]方面有较好的活性[7−9],其主要化学成分含有硫代葡萄糖苷类、黄酮类和苯丙素类等[10]。
近年来,对芜菁化学成分研究主要集中在乙酸乙酯部位,对芜菁的二氯甲烷部位研究较少,为了进一步研究芜菁的化学成分,探索芜菁二氯甲烷中的化学成分,促进其资源的开发和利用。
1. 材料与方法
1.1 仪器和试剂
旋转蒸发仪(上海亚荣生化仪器厂,型号:RE-5205;超导核磁共振仪(瑞士 Bruker 公司,型号:Bruker AC-300P);暗箱式三用紫外分析仪(上海嘉鹏科技公司,型号:ZF-20C);半制备高效液相色谱仪(美国 Agilent 公司,型号:1200 Series);反相ODS(日本三菱公司);柱层析硅胶(青岛海洋化工厂,批号:0220195);甲醇(美国默克公司,色谱级,批号:I10875507017);乙腈(美国默克公司,色谱级,批号:SHBN2542);石油醚(GENERAL-REAGENT公司,分析纯,批号:G842081);丙酮(重庆川东化工集团有效公司,分析纯,批号31025);甲醇(GENERAL-REAGENT公司,分析纯,批号:G75851C)。
1.2 植物来源
实验用芜菁由西藏昌都市类乌齐县雪域利美藏药材研发有限责任公司提供,经云南农业大学海梅荣教授鉴定为十字花科植物芜菁(Brassica rapa L.)的干燥根茎。
1.3 提取和分离方法
取干燥过的芜菁根茎30.0 kg粉碎,倒入大型回流提取罐中,按芜菁∶甲醇=1∶3加入甲醇进行回流提取4次,合并药液。提取液真空减压浓缩得到总浸膏9.73 kg。接着用水充分溶解甲醇提取物,二氯甲烷萃取,得到二氯甲烷部浸膏647 g。取二氯甲烷部浸膏加入300 g 硅胶(100~200目)拌样。3.0 kg柱色谱硅胶(100~200目),石油醚-丙酮(20∶1~1∶1)梯度洗脱,TLC分析合并得到13个部位(Fr.1~Fr13)。Fr.3经硅胶柱色谱(200~300目)用石油醚-丙酮(10∶1~1∶1)梯度洗脱,经ODS柱色谱用甲醇-水(30%~100%)洗脱,再经HPLC(45%甲醇水,tR:47.3 min)得到化合物1。Fr.4经硅胶柱色谱(200~300目)用石油醚-丙酮(10∶1~1∶1)梯度洗脱,得到Fr.4.1经制备TLC,再经HPLC(0~30 min,40%~100% 甲醇,tR:23.0 min)得到化合物2。Fr.4.4 经ODS柱色谱用甲醇-水(30%~100%)洗脱,得到Fr.4.4.3,再经HPLC(53%甲醇水,tR:46.7 min)得到化合物3。Fr.4.4.6 制备TLC(石油醚∶丙酮=7∶3)后经HPLC(67%乙腈水,tR:36.4、52.1 min)得到化合物5、6。Fr.2经硅胶柱色谱(200~300目)用石油醚-丙酮(10∶1~1∶1)梯度洗脱,得到Fr.2.4,再经制备TLC(石油醚∶丙酮=8∶2)得到Fr.2.4.1,经HPLC(85%乙腈水,tR:31.5 min)得到化合物4。Fr.5经硅胶柱色谱(200~300目)用石油醚-丙酮(10∶1~1∶1)梯度洗脱得到Fr.5.2经ODS柱色谱用甲醇-水(50%~100%)洗脱,制备TLC(石油醚∶丙酮=6∶4),再经HPLC(80%乙腈水,tR:41.7 min)得到化合物7。Fr.5.4经制备TLC(石油醚∶乙酸乙酯=8∶2),再经HPLC(80%乙腈水,tR:37.7 min)得到化合物8。Fr.5.4.1经制备TLC(石油醚∶丙酮=6∶1)得到Fr.5.4.1.2。HPLC(80%乙腈水,tR:46.1 min)得到化合物9。Fr.5.4.3经 HPLC(68%乙腈水,tR:25.3 min)得到化合物10。Fr.6经硅胶柱色谱(200~300目)用石油醚-丙酮(10∶1~1∶1)梯度洗脱,Fr.6.1经HPLC(45%甲醇水,tR:31.5 min、53.0 min)得到化合物11、12。Fr.6.4经制备TLC(石油醚∶丙酮=6∶1)得到Fr.6.4.1.1,HPLC(0~30 min,45%~100%甲醇,tR:26.1 min)得到化合物13。Fr.7经 ODS 柱色谱用甲醇-水(30%~100%)洗脱,得到Fr.7.3经硅胶柱(200~300目)在(石油醚∶丙酮=10∶1~6∶4)洗脱Fr.7.3.5,再经HPLC(80%乙腈水,tR:21.5 min)得到化合物14。Fr.7.4经TLC(石油醚∶丙酮=7∶3)得到化合物15和化合物16。Fr.7.7经ODS柱色谱用甲醇-水(30%~100%)洗脱得到Fr.7.7.5,再经制备TLC(石油醚∶丙酮=8∶2),得到化合物17。
2. 结果
化合物1:白色粉末。1H NMR (600 MHz,CDCl3) δ: 2.5 (3H,s,-CH3),6.88 (2H,d,J = 8.5 Hz,H-3,5),7.91 (2H,d,J = 8.7 Hz,H-2,6),9.35 (1H,br s,-OH);13C NMR (151 MHz,CDCl3) δ: 196.9 (C=O),160.0 (C-4),130.9 (C-1),130.48 (C-2,6),115.2 (C-3,5),29.7 (C-7),26.3 (-CH3)。以上数据与文献报道基本一致,故鉴定为1- (4 -羟基苯基)-2-丙酮[11]。
化合物2:黄色液体。1H NMR (600 MHz,CDCl3) δ: 9.02 (1H,s,OH),7.10 (2H,d,J = 8.4 Hz,H-5),6.80 (2H,d,J = 8.4 Hz,H-4),3.46 (1H,t,J = 7.3 Hz,H-1),3.35 (2H,t,J = 7.3 Hz,H-1′ ),2.65 (2H,t,J= 7.2 Hz,H-2),1.44 (2H,m,H-2′ ),1.28 (2H,m,H-3′ ),0.84 (3H,t,J = 7.4 Hz,H-4′ ); 13C NMR (151 MHz,CDCl3) δ: 154.7 (C-6),130.2 (C-4),129.5 (C-3),115.7( C-5),71.3 (C-1),69.5 (C-1′ ),34.7 (C-2),30.7 (C-2′ ),19.7 (C-3′ ),14.1 (C-4′ )。以上数据与文献报道基本一致,故鉴定为4-(2-丁氧基乙基)苯酚[12]。
化合物3:黄绿色油状物。1H NMR (600 MHz,CDCl3) δ: 7.61(1H,d,J =8.0 Hz,H-7),7.40 (1H,dt,J = 8.2 Hz,H-4),7.27(1H,t,J =7.5 Hz,H-6),7.21(1H,s,H-2),7.19 (1H,t,J = 8.0 Hz,H-5),4.07 (3H,s,N-OCH3),3.83 (2H,d,J =0.9 Hz,H-10). 13C NMR (151 MHz,CDCl3) δ :136.2 (C-1),126.0 (C-9),122.9 (C-2),120.2 (C-5),118.2 (CN),118.0 (C-4),111.5 (C-7),104.7 ( C-3),14.4 (C-10)。以上数据与文献报道基本一致,故鉴定为1-甲氧基-3-吲哚乙腈[13]。
化合物4:白色结晶。1H NMR (600 MHz,CDCl3) δ: 7.54(2H,d,J =8.6 Hz,H-6,6′ ),7.39 (2H,t,J =2.2 Hz,H-3,3'),7.16 (2H,m,J =8.6,2.5 Hz,H-5,5′ ),1.43 (9H,s,H-8~10,8′ ~10′ ),1.30 (9H,s,H-12~14,12′ ~14′ ); 13C NMR (151 MHz,CDCl3) δ: 147.8 (C-1,1'),146.9 (C-2′ ),146.9 (C-2),138.4 (C-4),124.4 (C3,3′ ),138.43 (C-4′ ),124.8 (C5,5′ ),118.6 (C-6),118.6 (C-6′ ),36.3 (C-7,7′ ),34.8 (C-11,11′ ),31.4 (C-8~10,8′ ~10′ ),30.2 (C-12~14,12′ ~14′ )。以上数据与文献报道基本一致,故鉴定为 2,2'-oxybis(1,4)-di-tert-butylbenzene[14]。
化合物5:白色粉末。1H NMR (600 MHz,CDCl3) δ: 4.18 (1H,dd,J =11.6,4.4 Hz,H-1a),4.12 (1H,dd,J =11.6,6.0 Hz,H-3a),3.65 (1H,dd,J =11.4,4.9 Hz,H-1b),3.57 (1H,dd,J =11.2,4.8 Hz,H-3b),3.90 (1H,m,H-2),2.35 (2H,t,J = 7.5 Hz,H-2′ ),0.88 (3H,t,J = 6.9 Hz,H-16′ ); 13C NMR (151 MHz,CDCl3) δ: 174.3 (C-1′ ),70.2 (C-2),65.1 (C-1),63.3 (C-3),34.1 (C-2′ ),31.9 (C-3′ ),30.1 (C-5′ ),29.6 (C-6′ ),29.6 (C-7′ ),29.6(C-8′ ),29.6 (C-9′ ),29.5 (C-10′ ),29.4 (C-11′ ),29.3 (C-12′ ),29.2 (C-13′ ),29.1 (C-14′ ),22.6 (C-15′ ),14.1 (C-16′ )。以上数据与文献报道基本一致,故鉴定为单棕榈酸甘油酯[15]。
化合物6:无色油状物。1H NMR (600 MHz,CDCl3) δ: 7.72 (2H,m,H-3,H-6),7.53 (2H,m,H-4,H-5),4.09 (2H,d,J = 6.7 Hz,H-1′ ),2.03 (1H,m,H-2′ ),4.30 (2H,t,J = 6.7 Hz,H-1′ ′ ),1.76 (2H,m,H-2′ ′ ),1.48 (2H,m,H-3′ ′ ),0.99 (3H,t,J = 7.4 Hz,H-4′ ′ ); 13C NMR (151 MHz,CDCl3) δ: 167.7 (C=O),167.6 (C=O),132.3 (C-1),132.2 (C-2),130.9 (C-4),130.9 (C-5),128.8 (C-3),128.8 (C-6),71.7 (C-1′ ),65.5 (C-1′ ′ ),30.5 (C-2′ ′ ),27.7 (C-2′ ),19.1 (C-3′ ′ ),13.7 (C-4′ ′ )。以上数据与文献报道基本一致,故鉴定为邻苯二甲酸-1-丁酯-2-异丁酯[16]。
化合物7:无色油状物。1H NMR (600 MHz,CDCl3) δ: 7.72 (2H,dd,J = 7.0,3.3 Hz,H-3,H-6),7.53 (2H,dd,J = 5.7,3.3 Hz,H-4,H-5),4.3 (4H,t,J = 6.7 Hz,H-1′ ),1.78 (2H,m),1.59 (4H,s,J = 7.5,H-3′ ),0.96 (6H,t,J = 7.4 Hz,H-4′ ); 13C NMR (151 MHz,CDCl3) δ: 167.7 (COO-),132.3 (C-1,2),130.9 (C-4,5),128.8 (C-3,6),65.5 (C-1′ ),30.5 (C-2′ ),19.1 (C-3′ ),13.73 (C-3′ )。以上数据与文献报道基本一致,故鉴定为邻苯二甲酸二丁酯[17]。
化合物8:黄色油状物。1H NMR (600 MHz,CDCl3) δ: 9.97 (s,CHO),8.31 (1H,d,J = 7.9 Hz,H-7),7.89 (1H,s,H-2),7.49 (1H,d,J = 8.1 Hz,H-4),7.39 (1H,t,J = 7.6 Hz,H-6),7.34 (1H,t,J = 7.5 Hz,H-5),4.20 (3H,s,OCH3); 13C NMR (151 MHz,CDCl3) δ: 184.1 (CHO),132.6 (C-7),131.7 (C-2),124.6 (C-5),123.5 (C-4),122.1 (C-3a),121.6 (C-7a),114.0 (C-3),108.7 (C-6),66.8 (-OCH3)。以上数据与文献报道基本一致,故鉴定为1-甲氧基-3-吲哚甲醛[18]。
化合物9:黄色油状物。1H NMR (600 MHz,CDCl3) δ: 7.70 (2H,dd,J = 5.7,3.3 Hz,H-3′ ,H-7′ ),7.53 (3H,dd,J = 5.7,3.3 Hz,H-5′ ,H-6′ ),4.22 (2H,dd,J = 11.4,5.9 Hz,H-1),1.68 (1H,d,J = 6.2 Hz,H-3),1.35 (1H,m,H-9),0.92 (1H,m,J =7.5 Hz,H-8),0.85 (1H,m,J =6.8 Hz,H-10); 13C NMR (151 MHz,CDCl3) δ: 167.7(C-1′ ),132.4 (C-2′ ),130.8 (C-3′ ),130.2 (C-5′ ),130.0 (C-7′ ),128.7 (C-4′ ),128 (C-6′ ),68.1 (C-1),30.5 (C-2),67.2 (C-3),22.9 (C-4),23.9 (C-5),23.7 (C-6),38.7 (C-7),11.1 (C-8),29.0 (C-9)。以上数据与文献报道基本一致,故鉴定为3,7-Dimethyl-n-octan-3α-ol-1-yl-benzoate[19]。
化合物10:无色固体。1H NMR (600 MHz,CDCl3) δ: 7.72 (2H,dd,J = 5.7,3.3 Hz,H-3,6),7.53 (2H,dd,J = 5.7,3.3 Hz,H-4,5),4.31 (4H,t,J = 6.7 Hz,H-1′ ,1′ ′ ),1.79 (2H,m,H-2′ ,2′ ′ ),1.55 (s,13H),1.44 (16H,m,8 x CH2),0.96 (6H,m,H-b′ ,b′ ′ ),0.90 (6H,t,J = 7.2 Hz,H-7′ ,7′ ′ ); 13C NMR (151 MHz,CDCl3) δ:167.7 (C=O),132.3 (C-1,2),130.9 (C-3,6),128.8 (C-4,5),65.5 (C-1′ ,1′ ′ ),31.4 (C-2′ ,2′ ′ ),30.5 (C-3′ ,3′ ′ ),29.7 (C-4′ ,4′ ′ ),29.5 (C-5′ ,5′ ′ ),22.9 (C-6′ ,6′ ′ ),19.18 (C-a′ ,a′ ′ ),14.1 (C-7′ ,7′ ′ ),13.73 (C-b′ ,b′ ′ )。以上数据与文献报道基本一致,故鉴定为邻苯二甲酸二( 2 -乙基)己酯[20]。
化合物11:白色针晶状。1H NMR (600 MHz,CDCl3) δ:5.35 (1H,m,H-6),5.02 (1H,dd,J =9.0、15.0 Hz,H -23),5.16 (1H,dd,J =8.5、15.0 Hz,H -22),3.52 (1H,m,H-3),0.92 (3H,d,J = 6.5 Hz,H-21),0.85 (3H,t,J = 6.5 Hz,H-29),0.87、0.82 (3H,each both,d,J = 7.5,H-26,27),0.68、1.01 (3H,d,J = 2.0 Hz,H-18,19); 13C NMR (151 MHz,CDCl3) δ: 37.2 (C-1),31.9 (C-2),71.8 (C-3),42.3 (C-4),140.7 (C-5),121.7 (C-6),31.8 (C-7),31.6 (C-8),50.1 (C-9),36.5 (C-10),21.1 (C-11),39.7 (C-12),42.2 (C-13),56.7 (C-14),24.3 (C-15),28.2 (C-16),56.7 (C-17),11.8 (C-18),19.3 (C-19),36.1 (C-20),18.7 (C-21),33.9(C-22),26.0 (C-23),45.8 (C-24),29.1 (C-25),19.8 (C-27),23.0 (C-28),11.9 (C-29)。以上数据与文献报道基本一致,故鉴定为β-谷甾醇[21]。
化合物12:黄色油状。1H NMR (600 MHz,CD3OD) δ: 4.36 (2H,d,J = 9.4 Hz,H-1,1′ ),3.25 (2H,dd,J =9.0、9.5 Hz,H-2,2′ ),3.17 (2H,dd,3.18 (2H,dd,J = 9.0、9.1 Hz,H-3,3′ ) ,3.08 (2H,dd,J =9.0、9.5 Hz,H-4,4′ ),3.14 (2H,m,H-5,5′ ),[3.62 (1H,dd,J = 12.0,5.3 Hz),3.84 (2H,dd,J = 12.0,1.8 Hz) ,H2-6,6′ ];13C NMR (151 MHz,CD3OD) δ: 90.6 (C-1,1′ ),81.0 (C-5,5′ ),78.1 (C-3,3′ ),71.2 (C-2,2′ ),70.0 (C-4,4′ ),61.6 (C-6,6)。以上数据与文献报道基本一致,故鉴定为TgSSTg[21]。
化合物13:黄色粉末。1H NMR (600 MHz,CD3OD) δ: 9.79 (1H,s,H-10),8.06 (1H,d,J = 7.8 Hz,H-4),8.01 (1H,s,H-2),7.38 (1H,d,J = 8.0 Hz,H-7),7.21 (1H,m,H-5),7.14 (1H,td,J = 7.6,1.2 Hz,H-6); 13C NMR (151 MHz,CD3OD) δ: 186.0 (C-10),138.3 (C-2),118.7 (C-3),124.3 (C-5),122.2 (C-6),120.9 (C-4),111.7 (C-7),137.5 (C-8),123.6 (C-9)。以上数据与文献报道基本一致,故鉴定为3-吲哚甲醛[22]。
化合物14:白色粉末。1H NMR (600 MHz,CDCl3)) δ: 7.55 (1H,d,J = 15.8 Hz,H-7),7.06 (1H,d,J = 2.0 Hz,H-2),6.95 (1H,dd,J = 8.2,2.1 Hz,H-3),6.80 (1H,d,J = 8.1 Hz,H-5),6.24 (1H,d,J = 15.8 Hz,H-8);13C NMR (151 MHz,CDCl3) δ: 173.6 (C-9),152.0 (C-7),149.6 (C-3),149.3 (C-4),127.9 (C-1),125.4 (C-6),18.0 (C-5),117.6 (C-2)。以上数据与文献报道基本一致,故鉴定为咖啡酸[23]。
化合物15:黄色粉末。1H NMR (600MHz,CD3OD ) δ: 6.17 (1H,d,J= 1.5 Hz,H-6),6.38 (1H,d,J= 1.5 H,H-8),7.82 (1H,d,J= 1.7 Hz,H-2 ),6.87 (1H,d,J=6.8 Hz,H-5 ),7.69 (1H,dd,J= 1.7,6.8 Hz,H-6 ); 13C NMR ( 151 MHz,CD3OD) δ:146.9 (C- 2),136.7 (C- 3),176.5 (C- 4),157.7 (C-5),99.1 (C-6),164.9 (C- 7),94.4 (C-8),162.3 (C-9),104.1 (C-10),121.4 (C-1′ ),115.7 (C- 2′ ),145.8 (C-3′ ),148.3 (C-4′ ),116.2 (C-5′ ),123.7 (C-6′ )。以上数据与文献报道基本一致,故鉴定为槲皮素[24]。
化合物16:淡黄色油状物。1H-NMR (600 MHz,CDCl3) δ: 7.67 ( 2H,m,H-2,6),7.72 (2H,m,H-3,5),4.22 (2H,t,J=6.6 Hz,H-1'),1.64 (2H,m,H-2'),1.28 (2H,m,H-3'),1.37 (2H,m,H-4'),0.86 (3H,d,J=7.2 Hz,H-5'),4.14 (2H,m,H-1′ ′ ),1.64 (1H,m,H-2′ ′ ),1.26 (2H,m,H-3′ ′ ),1.34 (2H,m,H-4′ ′ ),1.29 (2H,m,H-5′ ′ ),0.91 (3H,t,J=7.2 Hz,H-6′ ′ ),0.88 (3H,t,J=7.2 Hz,H-7′ ′ ); 13C NMR (CDCl3,150 MHz) δ: 131.6 (C-1),131.5 (C-2),128.5 (C-3,5),131.5 (C-4),131.4 (C-6),166.9 (C-7),166.4 (C-8),67.3 (C-1'),29.6 (C-2'),23.1 (C-3'),18.2 (C-4'),13.8 (C-5'),64.9 (C-1′ ′ ),38.0 (C-2′ ′ ),29.7 (C-3′ ′ ),28.2 (C-4′ ′ ),22.3 (C-5′ ′ ),13.2 (C-6′ ′ ),10.5 (C-7′ ′ )。以上数据与文献报道基本一致,故确定化合物auriculatumA[25]。
化合物17:白色固体。1H NMR (600 MHz,CD3OD) δ: 7.71 (1H,d,J= 8.7 Hz,H-5),7.41(2H,d,J = 8.7 Hz,H-2',6'),7.15 (2H,d,J = 8.6 Hz,H-3',5),6.53 (1H,dd,J = 8.7、2.3 Hz,H-6),6.34 (1H,d,J= 2.2 Hz,H-8),5.45 (1H,dd,J= 12.9,2.9 Hz,H-2),4.95 (1H,d,J = 1.59 Hz,H-1′ ′ ),3.90 (1H,dd,J =12.1,2.1 Hz,H-6"a),3.70 (1H,dd,J = 12.1,5.6 Hz,H-6"b),3.04 (1H,dd,J = 16.9,12.9 Hz,H-3a),2.73 (1H,dd,J= 16.9,3.0 Hz,H-3b); 13C NMR (125 MHz,CD3OD) δ: 193.1(C-4),166.8 (C-7),165.3 (C-8a),159.2 (C-4'),134.4 (C-1'),129.8 (C-5),128.7 (C-2',6),117.7 (C-3',5'),114.9 (C-4a),111.8 (C-6),103.8 (C-8),80.6 (C-2),44.9 (C-3); glucose: 102.1 (C-1′ ′ ),74.8 (C-2′ ′ ),78.1 (C-3′ ′ ),71.3 (C-4′ ′ ),77.9 (C-5′ ′ ),62.4 (C-6′ ′ )。以上数据与文献报道基本一致,故确定化合物甘草黄苷[26]。
3. 讨论
本试验通过硅胶柱层析、薄层层析和半制备HPLC等方法对芜菁甲醇提取物的二氯甲烷部分的化学成分进行研究,从芜菁中分离鉴定了17个化合物,包括3个苯丙素类衍生物:(1) 1-(4-羟基苯基)-2-丙酮、(2) 4-(2-丁氧基乙基)苯酚、(15) 咖啡酸;3个吲哚类生物碱化合物:(3) 1-甲氧基-3-吲哚乙腈、(8) 1-甲氧基-3-吲哚甲醛、(13) 3-吲哚甲醛;3个邻苯二甲酸衍生物:(6) 邻苯二甲酸-1-丁酯-2-异丁酯、(7) 邻苯二甲酸二丁酯、(10) 邻苯二甲酸二(2-乙基)己酯;硫苷类化合物:(12) TgSSTg;2个黄酮类化合物:(15) 槲皮素、(17) 甘草黄苷。5个其他类化合物:(4) 2,2′ -oxybis(1,4)-di-tert-butylbenzene、 (5)单棕榈酸甘油酯、(9) 3,7-Dimethyl-n-octan-3α-ol-1-yl-benzoate、(11) β-谷甾醇、(16) auriculatumA。其中1~5、8~9、12~13均为首次从该植物分离得到,进一步阐明了芜菁的化学成分组成,为芜菁药材后续研究提供物质及理论基础因此,对芜菁化学成分进行全面深入地研究,力争发掘出更多的活性成分,对于药用价值的发现及新药开发具有重大意义。
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